Metal-containing reactive monoazo dyestuffs containing a triazine group



United States Patent 3,354,140 METAL-CONTAININ G REACTIVE MON OAZO DYE-STUFFS CONTAINING A TRIAZINE GROUP Jakob Benz, Oberwil, Basel-Land, andHanspeter Uehlinger, Basel, Switzerland, assignors to Sandoz Ltd. (alsoknown as Sandoz AG), Basel, Switzerland No Drawing. Filed Dec. 11, 1964,Ser. No. 417,840 Claims priority, application Switzerland, Apr. 10,1959, 71,848/59 7 Claims. Cl. 260-146) ABSTRACT OF THE DISCLOSURE1:2-chromium and 1:2-cobalt complex compounds of monoazo dyestuffs ofthe formula wherein w is hydrogen or chlorine,

y is hydrogen, chlorine or nitro,

z is hydrogen, chlorine, bromine or nitro, at least one of w, y and zbeing different from hydrogen,

R is a monohalo-1,3,5-triazinyl-2-radical, and v n is 1 or 2,

are excellently suitable for dyeing, padding or printing fibers ofnatural cellulose or of regenerated cellulose.

This application is a continuation-in-part of our application Ser. No.297,670, filed July 25, 1963 (and abandoned since the filing of thepresent application) and relates to the 1:2 chromium and 1:2 cobaltcomplex compounds of the monoazo dyestuffs of the formula 3,354,140Patented Nov. 21, 1967 the group O is attached to the naphthalenenucleus in one of the positions 7 and 8 and the NH group is attached toone of the positions 3' and 4' of the phenylene nucleus.

The term lower in lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl,lower carboxyalkyl and lower sulfoalkyl means containing 1 to about 5carbon atoms; e.g. lower alkyl extends from methyl to amyl and alsoencompasses the branched isomers. However the preferred meanings are:

for lower alkylmethyl, ethyl;

for loyer hydroxyalkylp-hydroxyethyl, 18- or -hydroxypropyl;

for lower alkoxyalkylB-methoxyor p-ethoxyethyl;

'y-methoxypropyl;

for lower carboxyalkylcarboxymethyl, fi-carboxyethyl;

for lower sulfoalkyl-p? sulfoethyl, 'y sulfopropyl andfl-hydroxy-v-sulfopropyl. A series of especially valuable dyestuffscomprises the 1:2-chromium and 1:2-cobalt complex compounds of thedyestuffs of the formula s) m-l N X and hal have the above-definedmeanings, 7

each of R R and R is independently chlorine or nitro, only one of R andR being nitro, and m is one of the integers 1 and 2.

wherein The production of the new chromiumor cobalt-containing dyestuffsconsists in reacting with each other 1 mole of the diazo compound of'aZ-amino-l-hydroxybenzene of the formula z w (III) 1 mole of a couplingcomponent of the formula ri l 7 NH IV) wherein H represents anexchangeable hydrogen atom,

and l mole of a reactive component of the formula lial the reactionbeing conducted in such a manner that the diazo compound is introducedinto the position ortho to OH of the coupling component and the radicalhal (VI) replaces the hydrogen atom H of the coupling component,

hydrogen halide being set free; during or after the forma- 29 'tion ofthe dyestuffs they are treated with a chromiumor cobalt-yielding agent.A suitable procedure is as fol- -lows':' 1 mole of a monoazo dyestuff ofthe formula 1 hydroxy-3,4,6-trichlorobenzene, 2-amino-1-hydroxy-4- ehloro 5-nitro-, -4-ch'lono-6-nitroand -4-nitro-6-chlorobenzene and Z-arninO-1-hydnoXy-4,6-dinitrobenzene.

The coupling components used as starting materials are the 1amino-8-hydroxynaphthalene-3,6- and -4,6-disulfonic acids, 2amino-8-hydroxy1raphth a1ene-3,6-d-isulfonic acid, and the derivativesof these acids in which the amino group is acyl ated by ananrirrotbenzoyl radical.

The radical X is e.g. an amino group, a lower alkylamino group(methylamino, ethylamino, nor iso-propylamino, n-, isoor see. butylamino, nor isoamylamino), a (ii-(lower alky1)- amino group(dimethyltamino, d-iethylamin o), a lower hydroxyalkylamino group(Z-hydroxyethylamino, 2- or 3-hydroxypropylamino), a di-(lowerhpd-roxyal kylyamino group [di-(Z-hydroxyet-hyl)-amino, d-i-(2-hy-droxypropyl)amino], a lower 'alkoxyal kyl amino group(Z-methoxyethylamino, 2-ethoxyethylamino, 2- or 3-methox'ypropylamino,3- or '4-methoxybutylamino), a

lower carboxyalkylamino group (carboxymethylamino, a-

and fi-carboxyethylamino), a N-lower-alkyl-N-lower carboxyalkylaminogroup (N methyl N-canboxymethylamino), a lower sul-foalkylamino group(fi-sulfo-ethylamino), a N-lower alkyl-N-lower sulfoalkyl-amino group 1mole of a reactive compound of the Formula V and a chromiurnorcobalt-yielding agent are reacted with each other so that the reactivecompound of the Formula V reacts with the exchangeable hydrogen atom ofthe monoazo dyestuff (VII) and the chromiumor cobaltyielding agentreacts with theortho-ortho-dihydroxyazo grouping.

Instead of the reactive component of the Formula V it is also possibleto employ cyanuric chloride or bromide and to replace afterward one ofthe remaining chlorine or bromine atoms by the radical X.

A modification of this procedure consists in coupling in ortho-positionto the hydroxy group 1 mole of the diazo compound of an amine of theFormula III with 1 mole of a coupling component of the formula Insteadof the coupling component of the Formula VIII it is also possible toutilize a coupling component of the formula I he]. on I NH oc Q mg ml CN Nu? e 1 and afterward to replace one of the halogen atoms by the 7(N-methylor N ethyl -N-sulfoethylamino), a phenylamino group, a N-loweralkyl-N-phenylamino group (N- methylor N-ethyl-N-phenylamino), a N-lowerhydroxyalkyl-N-phenylamino group (N-B-hydroxyethyl-N-phenylamino), acarboxyphenylamino group (2-, 3- or 4-carboxyphenylamino), a monoordisulfophenylamino group (2-, 3- or 4-monosulfophenylamino, 2,4-, 2,5-or 3,5-disulfophenylamino), a monoor disulfonaphthylamino group (4-, 6-or 7-sulfo-, -3,6-, -4,6-, -4,7- or -5,7-disulfonaphthyl-l-amino, 5-,6-, 7- or 8-sulfo-, -4,7-, '-4,8-, -6,8- or-5,7-disulfo-naphthyl-Z-amino), a lower 'alkylphenylamino group (2-, 3-or 4-methy1- or -ethylphenylamino), a lower alkoxyphenylamino group (2-,3- or 4-rnethoxyor -ethoxyphenylamino), a chlorophenylamino group (2-,3- or 4-chlorophenylarnino), a cyclo- (VIII) hexylamino group, amethylcyclohexylamino group (2-, 3- or 4-methylcyclohexylamino) or abenzylamino group.

The reaction of the reactive component of Formula V with the. aminogroup of the coupling component of Formula IV or of the monoazo dyestufiof Formula VII is carried out e.g. at temperatures of about 30 to 60 C.and in the pH-range of about 3 to 7, preferably at 4 to 6, in thepresence of an acid-binding agent which can be added in the form of apowder or of an aqueous solution. Examples of suitable binding'agentsare e.g. sodium acetate, bicarbonate, carbonate or hydroxide or thecorresponding potassium or lithium compounds. It is also possible toreact the amino group first with cyanuric chloride or bromide e.g. at atemperature of 0 to about 10 C. and a pH value comprised between about 3to 7, and then to react one of the remaining chlorine or bromine atomswith ammonia or a primary or secondary amine, the reaction being carriedout under the same conditions as described above for the reactivecomponent of Formula V or with two equivalents of amine, especiallyammonia, which acts at the same time as amine and as acid-binding agent.The addition of small amounts of a wetting or emulsifying agent to thereaction mixture can accelerate the rate of reaction.

The coupling of the diazo compound of an amine of the Formula III with acoupling component of Formula VIII is carried out in alkaline medium,preferably at temperatures of 10 C.

The monoazo dyestuffs are converted into their chromium or cobaltcomplex compounds preferably in aqueous solution or in an organicmedium, e.g. formarnide, or in the concentrated aqueous solution of analkali metal salt of a low molecular aliphatic monocarboxylic acid. Itis of advantage to proportion the reactants so that an amount ofmetal-yielding agent containing less than two but at least one atom ofmetal acts upon two molecules of the monoazo dyestuff.

Suitable chromium compounds are e.g. chromic fluoride, chromic sulfate,chromic formate, chromic acetate, chromic potassium sulfate or chromicammonium sulfate. The chromates, e.g. sodium or potassium chromate orbichromate, are also eminently suitable for metallizing the monoazodyestuffs. It is advantageous to work here in a strongly causticalkaline medium, to which reducing substances may be added if desired.

Cobaltous formate, cobaltous acetate and cobaltous sulfate are examplesof suitable cobalt compounds. If metallization is effected in theconcentrated aqueous solution of an alkali metal salt of a low molecularaliphatic monocarboxylic acid, water-insoluble metal compounds can beused, e.g. cobalt hydroxide or cobalt carbonate.

It is especially advantageous to carry out metallization in aqueous oralkaline medium to which the metal compounds are added in presence ofcompounds which maintain the metal dissolved in complex combination incaustic alkaline medium; examples of such compounds are tartaric acid,citric acid and lactic acid.

The metalcomplex compounds obtained are precipitated from aqueous mediumby the addition of salt, if desired after running the organicmetallizing solution into brine, and are subsequently filtered off,washed if necessary and dried.

The metal-containing azo dyestuffs thus obtained are homogenous metalcomplex compounds in which essentially one atom of metal is linked totwo molecules of the monoazo compound. The metal complex compounds areso-called 2:1 complexes in which one molecule of the monoazo compound islinked with approximately 0.3 to 0.7 atom of metal.

The new chromiumor cobalt-containing reactive dyestuffs are suitable fordyeing, padding or printing fibers of natural cellulose (e.g. cotton,linen, hemp) or of regenerated cellulose (viscose filament yarn andstaple fiber, cuprammonium rayon) in violet, dark blue and black shades.

The dyestuffs are dyed, padded, printed or fixed on cellulose fibers inan alkaline medium, e.g. in presence of sodium carbonate or bicarbonate,sodium or potassium hydroxide solution, sodium metasilicate, sodiumborate, trisodium phosphate, ammonia etc. It is often an advantage toadd a mild oxidizing agent such as sodium l-nitrobenzene-3-sulfonate tothe dyebath, padding liquor 'or printing paste, in order to precludereduction eflects. Normally, the dyestuffs are fixed on cellulosicfibers by heat treatment.

If strong alkalis such as sodium or potassium metasilicate or hydroxideare employed it is also possible to fix the dyestuffs to the cellulosefibers at lower temperatures e.g. 20 to 40 C., with fixation timesvarying from several hours for light shades to about 50 hours for strongshades.

The dyeings and prints on cellulose fibers are notable for theirexcellent fastness to wet agencies, which is due to the formation of astable chemical linkage between the dyestuff molecule and the cellulosemolecule. Often the total amount of dyestutf applied does not take partin the reaction with the fiber and in such cases the unreacted dyestuifis removed from the fiber by suitable after-treatment, e.g. washingand/or soaping, if necessary at higher temperatures. For this purposesynthetic detergents can be used, e.g. alkylarylsulfonates, sodiumlauryl sulfate, sodium lauryl polyglycol ether sulfate and monoanddialkylphenylpolyglycol ethers.

The new dyestuffs are well soluble in water giving solutions stable tosalts and to hard water and therefore possess the great advantage thatthe non-fixed portion of dyestuff can be easily washed out of the printsor paddyeings and that the printing pastes or padding liquors are stableto storage.

The possibility given by the substituent X and the bridge member NH- ofincreasing the molecular weight and/or the number of water-solubilizinggroups permits to adapt each dyestuif to the particular applicationintended. For instance a dyestufr which contains the bridge member andas X an amino group or a methylamino group is suitable for theexhaustion dyeing process, whereas for padding or printing purposes adyestutf in which n is 1 and X is an amino group or a methyl amino groupor n is 2 and X is a sulfoethylamino or a sulfophenylamino group ispreferred.

The dyeings and prints on fibers of natural or regenerated cellulose arenotable for their excellent fastness to light, washing, water,perspiration, alkali, organic acids such as acetic acid and tartaricacid, crocking and dry cleaning.

The dyestuffs reserve acetate, triacetate and polyethylene terephthalatefibers.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 52.8 parts of the monoazo dyestuff sodium l-hydroxy- .2 (2'hydroxy-S'-nitrophenylazo)-8-aminonaphthalene- 3,6-disulfonate aresuspended in 300 parts of water at 75. A solution of 14.5 parts ofcobaltous sulfate heptahydrate in 40 parts of water is dropped into thesuspension in the course of 30 minutes and at the same time a dilutesodium carbonate solution is dropped in to maintain the pH value of thereaction mass between 5.0 and 6.0. After the addition of the cobaltoussulfate solution the mass is stirred for a further hour at 75, afterwhich the dyestulf is precipitated with sodium chloride and filteredoff.

The cobalt complex compound is dissolved in 300 parts of water and at40, 34.5 parts of sodium 3-(4,6'-dichloro 1',4,5'triaZinyl-2-amino)-benzene-1-sulfonate are added. The pH value of thereaction solution is maintained between 4.0 and 6.0 by dropwise additionof a dilute sodium carbonate solution. After stirring for 4 hours at4045 condensation is completed. By the addition of sodium chloride thedyestuff is precipitated and is then filtered off and dried in vacuo. Itis a dark powder which dissolves in water with a dark blue coloration.

Cotton cretonne is printed at room temperature with a paste of thefollowing composition:

Parts Dyestuif obtained according to the foregoing details 65 Urea Water355 Sodium alginate thickening (3%) 450 Sodiuml-nitrobenzene-3-sulfonate 10 Sodium bicarbonate 20 7 The printed fabricis dried at 50, steamed for minutes at 102-104, rinsed in cold and warmwater, soaped at the boil, rinsed again and dried. A reddish black printwith good light and wet fastness is obtained.

disulfonate are stirred into 350 parts of water. At 80, 30 parts ofcrystallized sodium acetate and 30 parts of crystallized chromicpotassium sulfate are added and the mixture is heated for 24 hours withreflux. Subsequently the dyestuff solution is cooled to 45 16.5 parts of2- arnino 4,6 dichloro 1,3,5-triazine are added and it is stirred for afew hours at 50 with dropwise addition of dilute sodium carbonatesolution to maintain the pH value at 4.5-5.5. On completion ofcondensation the dyestuff is precipitated at 50 by the addition ofsodium chloride and filtered off, dried and ground. It is a black powderwhich dissolves in water to give dark blue solution.

A cotton fabric is impregnated on a pad with a solution of PartsAbove-described dyestufit' 8 Urea 20 Sodium carbonate 2 Water 100Example 3 34.1 parts of the monosodium saltl-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 200parts of water by the addition of dilute sodium hydroxide solution at 50and a pH value of 4.8-5.0. With vigorous stirring 16.5 parts of2-arnino-4,6-dichloro-1,3,5-triazine are added, then the reaction mediumis heated at 60 for 5-6 hours, during which time its pH is maintained at4.0-4.2 by dropping in dilute sodium carbonate solution. On completionof condensation the reaction mass is brought to a temperature of 20 byexternal cooling and 10.6 parts of sodium carbonate in 50 parts of waterare added. Over the next minutes this solution is run into a suspensionobtained by diazotization of 14.4 parts of2-arnino-l-hydroxy-4-chlorobenzene and neutralized with sodiumcarbonate. After stirring overnight the monoazo dyestuff is filtered offand the residue washed with water. The dyestufi paste is suspended in500 parts of water at 80 and at this temperature 16 parts of cobaltoussulfate heptahydrate are added. The temperature is subsequentlymaintained at 94-97 for 2 /2 hours, a constant pH of 5.0-6.0 beingmaintained by dropwise addition of a dilute sodium carbonate solution.The dyestuff is precipitated by the addition of sodium chloride,filtered off, dried at 70 and ground to give a dark powder whichdissolves in Water with a blue coloration.

Mercerized cotton sateen is printed with a paste of the followingcomposition:

Parts Dyestuif obtained according to the foregoing details 60 Urea 100Water. 360 Sodium alginate thickening (3%) 450 Sodiuml-nitrobenzene-3-sulfonate 15 Sodium carbonate 15 The print is dried,steamed for 10 minutes at 102-104, rinsed in cold and warm water, soapedat the boil, rinsed again and dried. It is of a reddish navy blue shadepossessing good light and wet fastness.

Example 4 The 1:2-chromium complex compound obtained from 51.8 parts ofthe dyestuff sodium1-hydroxy-2-(2'-hydroxy-5-ch1oro-phenylazo)-8-amino-naphthalene-3,6disulfonate as described in Example 2 is dissolved at 20 in 400 parts ofwater and the solution is cooled to 0. 18.5 parts of finely dispersedcyanuric chloride are added and the pH value of the reaction solution ismaintained between 3.0 and 4.0 by dropwise addition of a dilute sodiumcarbonate solution. After stirring for 3 hours at 0, condensation iscompleted. The solution is heated to 45 and 17.3 parts of3-aminobenzene-l-sulfonic acid dissolved in parts of water and therequisite amount of sodium hydroxide solution to give the pH value 6.0are added. The pH value of the reaction solution is maintained between5.0 and 6.0 by dropping in a dilute sodium carbonate solution. Afterstirring for 1 hour at 45 condensation is completed. The dyestuff isprecipitated by the addition of sodium chloride and filtered off. Ondrying it is obtained as a dark powder which dissolves in water with adark blue coloration.

Mercerised cotton sateen is printed with a paste of the followingcomposition:

Parts Dyestulf obtained according to the foregoing details 65 Urea 100Water 353 Sodium alginate thickening (3%) 450 Potassium carbonate 20Sodium hydroxide solution (30%) 2 Sodium l-nitrobenzene-3-sulfonate 10The dried print is steamed for 10-15 minutes at 102- 104 andsubsequently rinsed in cold and warm water, soaped at the boil, rinsedagain and dried. A navy blue print with good light and wet fastness isobtained.

Example 5 Parts Above dyestuff 50 Urea 200 Water 275 Sodium alginatethickening (4%) 450 Sodium l-nitrobenzene-3-sulfonate 10 Sodiumcarbonate 15 The print is dried and treated in dry heat for 1 minute at200 or 10 minutes at then rinsed in cold and warm water and soaped atthe boil. After further rinsing and drying a navy blue print of goodlight and wet fastness is obtained.

The followmg table glves detalls of further chromlumphng components 1nColumns (I) and (II), by the meanor cobalt-contammg react1ve dyestufiswh1ch were oblngs of hal and X 1n Columns (III) and (IV), by the tamedaccordmg to the detalls of Examples 1 to 5 and metal used for metalcomplex formatlon 1n Column (V) are denved from monoazo dyestuffs of theFormula I. and by the shade of the pad dyemgs and prmts on cotton In thetable they are charactenzed by the dlazo and cou- 5 1n Column (VI).

Diazo Component Coupling Component Metal Hal X Shade on Cotton Ex. No..

(I) (II) (I 6 l-nmino-2-hydroxy-5-nitroben-1-hydroxy-S-amlnonaphthalene- C0 Cl 4-sulfophenylamlno 'Reddish black.

zene. 3,6-disulfonic acid.

01 Graenish black. hydroxy-8-(4'-aminobe y Cr C1 D0.amino)-naphthalene-3,6-disulfonic acid .do C0 C1 Methylamino. Navy bl doC0 C1 2-su1foethy1amlno Do. l-hydroxy-S-aminonaphthalene- Cr 014-sulfopl1enylamino D0.

3,6-dlsulf0nlc acid. d0 Cr B1 H-110- Do. .do do C0 C1 Ethylamlno Rgddlshna ue. Cl 4-methoxyphenylamino. Do. Cl Z-carboxy-ethylamino Do.

l-amlnoy ydr y hloro-3- Cl N-methyl-N-2-sulfoethyl Navy blue.

nitrobenzene. ammo. 18 -d0 C1 ,5-disulfophenylamlno Rgtlidlsh navy ue.19 1-&min0-2-hydr0xy-3,5- Cl Dimethylamino Reddlsh black,

dlnitrobenzene. 20 do do Cr 01 Phenylamino Greem'sh bla 21 do1-hydroxy-8-amino-nephtha- Co Cl -hydr0xyethylamino Reddish bla k,

lene-3,5-disu1fonle acid. 22 1-am n02-hydroxy-5-chloro-4- d0 C0 C14-SHII0naphthyl-1-amin D nitrobenzene. 23 d0 do Cr Cl 1 0py1amlnoGreenlshblagk, 24 .do 1-hydroxy-7-amlnonaphthalene- Cr Cl Ammo D0,

3,6-disulfonic acid. 1-amin0-2-hydroxy-5-nitrodo {Cr 01-hydroxyethy1amlno Gray.

benzene. C0 C1 O IliSh violet. 26 l-z a mino-z-h drox -echlomdo C0 C1ydr0xypropylamino Violet enzene. 27 l-8II1iI10-2-hydroxy-5-chl0ro-3-.....do Cr C1 -S 1 f0phenylamino Navy bl nitrobenzene. 23lmino-2-hydroxy-3-chloro-5- ....d0 Cr 01 3-Su1f0phenylamino Blulsh gray,

nitrobenzene. 29 1-amino-2-hydroxy-3,5. .do Cr C1 Methylammo Do.

dx'nltrobenzene. 0 1-8mln0-2-hydroxy- 1-11ydr0xy-8-amlnouaphtha- Cr 013-hydr0xybutylamino Greenlsh black.

nitrobenzene lene-3,5-disulfonic acid.

do Cr Cl 2- ethylphenylamlno Do. Br Methy1amino Do.1-9,!1111'10-2-11ydroxy-3j- Cl D1ethylamino Blulsh black.

dinltrobenzene. 34, do Cl 2-ethoxyethylamino D 1-amin0-2-hyd10xy 4 Cl2-l1ydr0xypropylamin Greenish black.

nltrobenzene. V 3 do 1- yd1'0Xy-8-amin0- Cr 01 4-Inethy1phenylamino D0.

ne ahthalone-3,6-dlsulfonlc I 301 37 .do do C0 C1 2- rboxyphenylamlnbReddlsh bla k, 1.a 2. Cl 3-ch1orophenylamino Do.

nltrobenzene.

C1 Benzylamlno D0. 7

Cl n-Amylemino Greenish bla k QI'DIIIO. v 43 1-emin0-2-hydroxy-3,5,6- ClAmmo Navy bl trichloro-benzene. 44 do l-hydroxy-S-amlnonaphtha- Cr C1Dlmethylamlno Do.

. lone-3,5-dlsulfonle acid. 1 l I l-amln0-2-hydroxy-3,5- do Or 01Phenylamlno .7 Do.

dlchlorobenzene.

l-hydroxy-B-emlnonaphtha- C0 C1 N-methyl-N-phenylamlno 0.

lane-3 6-disulf0nlc acid.

Cr Carboxymethylemino D0. -amino-naphthe- Cr C1 Ethylamino Do.1ene-3,6-disulfonic acid. 1-amlno-2-hydroxy-4,5-l-hydroxy-8-amlnonephtha- Cr Cl 3-methoxypropylamino N avy blue.

dichlorobenzene. lene-3,6-dlsulfoulc acid. .do 00 C1 Amino Reticlldishnavy ue. 1-amino2-hydroxy-5- do C1 C1 Dl-(2 -hydroxyethyl) N avy blue.bromobenzene ammo. do do C0 C1 Amino Rgclldlsh navy I ue. dol-hydroxy-8-amlnonaphthalene- C0 C1 n-Butylamino Do.

3, 5-disulfonie acid.l-amino-2-hydroxy-5-ehlorol-hydroxy-S-(4-amlnobenzoyl- C0 C1N-methyLN-ilsulfoethyl- D0.

benzene. amino) -naphtha1ene-3, fi-diamino.

I sulfonic acid. d0 d0 Cr Cl 4,7-dlsull'onaphthyl-2-amlno Navy blue.

01 4,fi-disulfonaphthyl-l-amino. D0. -Cl 2, 4 disulfophenylaminoGreenlsh black. l-hydroxy-B-(3'-amiuobenzoyl- Cl5,8-mcnosulfonaphthyl-2- D0.

amino)-naphthalene-3, 6-diamino. sulfonic acid. C0 C1Di-(2-hydroxypropyD-emlno. Reddlsh black.

Br 3-sulf0phenylamino Do.

C1 Z-hydroxypropylamlno Greenlsh black.

01 N-methyl-N-carboxy- D0.

methylamino.

E N Diazo Component Coupling Component Metal Hal X Shade on Cotton 631-amino-Z-hydroxy-S-ehloro- 1-l1ydroxy-8-(3-aminobenznyl- Cr Cl4,8-dlsulfonephthyl-2- Navy blue.

benzene. amino)-uaphthalene-3, fi-diammo.

sulfonic acid. 64 .d do 00 Cl 4-carboxyphenylamino Rg ldlsh navy He...d0 l-hydroxy-S-(3'-amlnobenzoyl- 00 Cl 6-sulfonaphthyl-2-amlno. Do.

amino)-naphtl1alene-3, 5-disulfonle acid. 7 66 -d0 "do Cr 01 MethylamlnoNavy blue. 67 1-amino-2-hydr0xy-5-ehloro-3- do Cr Cl6,7-monosulfo-naphthyl-l- D0.

nltro-benzene. amino. 68 l-amine-2-hydroxy-5-nitr0bendo Cr 016,8-dlsulf0naphthyl-2- Greenlsh black.

zene. am 0. 69 ..do 1-hydroxy-7-(3-am1nobenzoy1- Cr 013-sulfophenylamlno D0.

amlno)-naphthalene-3,6- disulionle acid. 70 do do Co 01 Amino Redd shblack. 71 1- ln0-2-hydr0xy-5-chloro- .do C0 C1 4,7-disulfonaphthyl-1-Reddlsh navy benzene. amino. blue. 72 do do C0 C1fi-sullonaphthyl-l-amino o. 73 .do l-hydroxy-7-(4-aminobenzoy1- Or 017-sn1Ionaphthyl-1-amino... Navy blue.

amino)-naphthalene-3,6- disulionic acid. 74 d0 do 00 Cl2-sulfoethylamlno RigdlSh n vy ue. 75 1- in0-2-hydroxy-5-nitrodo C0 C13,6-disulf0naphthyl-1- Reddish black.

benzene. amino. 76 1-an in0-2-hydr0xy-5-0hl0r0-3-l-hydroxy-B-aminonaphthalene- Cr 01 Amino Violet.

mtrobenzene. 3,6-disulf0nic acid. 77 .d0 1-hydroxy-S-amlnonaphthalene-Or Cl Q-methoxyethylamlno Navy blue.

3,5-disulf0nic acid. 78. .do clo Cr Br Amino D0. 791-1111ino-2-hydroxy-5-chlorodp Cr 01 4-methy1cye1ohexylamlno. Do.

enzene. 80 .d0 do Cr 01 N-2-l1ydroxyethyl-N- D0.

phenylamlno. 81. 1innno-2hydroxy-5-nitrodo Co 01 3-methoxybuty1amlnoReddlsh black.

enzene. 82 do l-hydroxy-S-aminonephthalene- C0 C1 4-chlorophenylamlnoD0.

3,6-disulf0nlc acid.

(1 Cr 01 4-ethoxyphenylamlno Greenlsh black.

01 3-methylphenylamino... Do. Cl Z-methoxypropylamlno Do. Cl7-sulfonaphthyl-2-amlno... D0. dn 7 O1 N-ethyl-N-phenylamlno Do.1-amino-Z-hydroxy-E-ehloro- Cl N-ethyl-N-2-sulfoethyl- Navy blue.

benzene. amino. 89 (in fi Cr 01 Isoamylamino", Do. 901-amlno-2-hydroxy-3-chloro-5- -do Cr 01 5-sulI0naphthy1-1-amino. Do.

nitrobenzene. 91 1%Jmino-2 -l1ydroxy-4-nitrodo Cr Cl Amino Greenlshblack.

enzene. 92 0 Cl Gyclohexylamlno Reddlsh black. 93l-aminmZ-hydroxy-S-nitro- Cl Sec-butylamlno. Do.

benzene. 94 ..do Cl N-methyl-N-Z-carboxy- D0.

ethylamlno. 95 dn d0 01' C1 fi-sulfonaphthyl-l-amlno...-. Greenlshblack. 06 do 1-hydroxy-8-(4-amlnobanzoy1- Cr 01 3,5-disu1fophenylamlnoD0.

ammo)-naphthalene-3,6dlsulfonic acid. 97 .-.do Cr 015,7-dlsulfonaphthyl-l-amlno. D0. 98 f fin 1 00 Cl5,7-disulionaphthyl-2-amlno Reddish black. 991-aImn0-2-hydr0xy-5-chl0ro- 1-hydroxy-8-aminonaphthalene- C0 C1Isopropylamlno Reddish navy benzene. 3,6-dlsulfonlc acid. blue.

d o Cl 4'methoxybutylamlno Do. 01 Z-methoxyphenylamlno- Do. ClS-carboxyphenylamino Navy blue 01 4-ethylphenylamino D0. 01Isobutylamino Do. Cl Z-hydroxy-B-sulfopropyl- Do.

amino.

Formulae of representatlve dyestuffs of the foregomg Examples 2 and 5examples are as follow:

Example 1 60 I C1 0 N 65 H 00 N HOaS N (3; 11+

N NH-O 0-01 70 l H 1 NH-C 0-01 N N H035 HOaS (I) H038 \C L Having thusdisclosed the invention what we claim is: 1. A member selected from thegroup consisting of the 1:2-chromium and the 1:2-cobalt complexcompounds of the monoazo dyestulf of the formula wherein w is a memberselected from the group consisting of hydrogen and chlorine, y is amember selected from the group consisting of hydrogen, chlorine, andnitro, Z is a member selected from the group consisting of 5 hydro-gen,chlorine, bromine and nitro, at least one of w, y and 2 being differentfrom hydrogen, hal is a member selected from the group consisting ofchlorine and bromine, X is a member selected from the group consistingof amino, lower alkylamino, di-(lower alkyl)-amino,

lower hydroxyalkylamino, di-(l0wer hydroxyalkyD- amino, loweralkoxy-lower alkylamino, lower carboxyalkylamino, N-lower alkyl-N-lowercarboxyalkylamino, lower sulfoalkylamino, lower hydroxysulfoalkylamino,N-lower alkyl-N-lower sulfoalkylamino, phenylarnino, N-loweralkyl-N-phenylamino, N lower hydroxyalkyl N phenylamino, carboxyphenylamino, monosulfophenylamino, disulfophenylamino,monosulfonaphthylamino, disulfonaphthyl amino, lower alkylphenylamino,lower alkoxyphenylamino, chlorophenylarnino, cyclohexylamino,methylcyclohexylamino and benzylamino, n is one of the integers 1 and 2,

N the group NH fi NH oc-Q N N 3 NH- HO s a C is attached to thenaphthalene nucleus in one of the porim, 2 sitions 7 and 8 and the NH--group is attached to one of the positions 3' and 4 of the phenylenenucleus. Example 8 2. The dyestuif of the formula ozN- -0 roN-@-0-- I NN Go H'- Or 11+ ll HOaS N 303's N NHC C-Cl -NH0 0-01 I Ilr N N N HOzSH033 \I/ 1 NH: J2

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE 1:2-CHROMIUM ANDTHE 1:2-COBALT COMPLEX COMPOUNDS OF THE MONOAZO DYESTUFF OF THE FORMULA